CN101284212A - Heavy metal dispersed and supported liquid membrane separating and recovering method - Google Patents
Heavy metal dispersed and supported liquid membrane separating and recovering method Download PDFInfo
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- CN101284212A CN101284212A CNA2008100183280A CN200810018328A CN101284212A CN 101284212 A CN101284212 A CN 101284212A CN A2008100183280 A CNA2008100183280 A CN A2008100183280A CN 200810018328 A CN200810018328 A CN 200810018328A CN 101284212 A CN101284212 A CN 101284212A
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Abstract
The invention discloses a separation and recovery method of a dispersion supporting liquid membrane of heavy metal. The method is implemented according to the following steps: in the membrane pretreatment step, liquid membrane solution is utilized to soak a polymer supporting membrane, then the surface of the polymer supporting membrane is dried, and the polymer supporting membrane is utilized to separate a feed liquid pool and a resolving pool; in the liquid membrane transport step, a feed liquid phase containing heavy metal ions is injected in the feed liquid pool, and the pH of the feed liquid phase is controlled; a membrane phase and a resolving phase which are weighted respectively are mixed to form a dispersion phase, the total volume of which corresponds to that of the feed liquid phase; the dispersion phase is injected into the resolving pool; the feed liquid pool and the resolving pool are stirred, and the concentration in the resolving pool is analyzed by timing sampling; in the separation and recovery step, when the concentration in the resolving pool reaches the recovery concentration, the stirring is stopped, and the dispersion phase is stood to lead the dispersion phase to be layered, wherein, a water phase is the separated and recovered heavy metal ion solution. Without adding any surface active agents, the separation and recovery method keeps the stability of a supporting liquid membrane system, and increases the membrane mass transfer efficiency.
Description
Technical field
The invention belongs to the separation and recovery technology field of heavy metal, relate to a kind of method of carrying out the metal separation recovery, be specifically related to the dispersed and supported liquid membrane separating and recovering method of a heavy metal species with dispersed and supported liquid membrane.
Background technology
Plating is the mainstay industry of China, relates to machine-building, electronics light industry, Aero-Space, field of petrochemical industry such as copper facing, zinc-plated, nickel plating, cadmium plating, about 400,000,000 tons of the waste liquid that contains heavy metal of the annual discharging of national electroplating industry.The recovery of China's lead at present is about 80%, and external plumbous recovery reaches more than 95%.Heavy metal can not but can be become hundred times of enrichments thousandfold by biodegradation on the contrary at nature under the biological magnification of food chain, enter human body at last.Although some heavy metal such as copper, zinc, cobalt, nickel etc. are the needed trace elements of vital movement, most of heavy metal is not that vital movement institute is necessary as lead, cadmium etc., and all heavy metals all can be to the human body toxic side effect above finite concentration.Strong interactions take place in heavy metal energy and protein and enzyme etc. in human body, and they are lost activity, and also may accumulate in some organ of human body and cause slow poisoning.Therefore the separation and recovery technology of heavy metal obtains people's extensive attention.
The separation method of existing heavy metal has solvent extraction, separation by precipitation, ion-exchange, liquid membrane separating method etc.Wherein solvent extraction is one of isolation technics that is most widely used, but this technology is subjected to the restriction of mass transfer balance, separation equipment is bulky, and in actual applications, the extraction and two the different mass transport processes of genus of stripping need be carried out in two different reactors, will use a large amount of organic solvents simultaneously, increased the complexity and the operation easier of technology, cost is higher.Separation by precipitation is removed heavy metal by precipitation reaction with precipitation form, and sedimentary harmless processing is miscellaneous, is difficult for regeneration or resource.Ion exchange separation process is subjected to the restriction of ion-exchanger exchange capacity.Get a kind of non-equilibrium mass transport process that is taken at one, carries out simultaneously with back extraction and liquid membrane separating method is a kind of treasury, have adaptability and excellent selectivity widely.
Existing a kind of emulsion liquid membrane separates the method for the chromium in the waste water, comprises the following steps: 1), the system breast: with surfactant, flowing carrier and solvent, high-speed stirred makes stable white emulsion; 2), mix: emulsion and pending K
2Cr
2O
7Solution mixes by a certain percentage, and stirring at low speed makes chromium fully extract; 3), breakdown of emulsion: after the chromium in the pending liquid is fully extracted, change separatory funnel over to, take off the content that the colourless water of layer surveyed chromium, monitor back up to standard discharging.Oil reservoir is the emulsion of oil phase and interior water, utilizes the water behind the microwave technology breakdown of emulsion to be chromic salts.Though the method that this emulsion liquid film separates has high separative efficiency, need miscellaneous operations such as system breast and breakdown of emulsion, the cost of equipment height.
1), hollow membrane soaks into existing a kind of method of utilizing hollow fiber renewal liquid membrane can realize extraction at the same level and the needs of stripping, and may further comprise the steps:: respectively with liquid film mutually and deionized water flow through membrane contactor, the micropore of film is soaked into extraction phase; 2), feed liquid and extraction phase are by 5～50: 1 volume ratio mixes in material liquid tank, with peristaltic pump this mixed liquor is sent into film organ pipe journey (tube side) inlet, and it is flowed in hollow fiber conduit; With pump film device shell side (shell side) inlet is sent in back extraction mutually, made it interbank mobile at doughnut.Flow out unnecessary organic facies from the tube side outlet, be collected in the residual jar of collection,, loop back the tube side inlet, repeated use through simple clarification phase-splitting.Though this method has realized extraction and reextraction and has carried out simultaneously, eliminated the liquid film life problems that supported liquid membrane runs off and causes because of coating solution, need in advance in the feed liquid in-tank mixing but its shortcoming is feed liquid phase and extraction phase, when the concentration of solute was hanged down, extraction phase was prone to emulsification, cause fenestra to stop up, membrane resistance increases, and mass-transfer efficiency descends, alternate leakage problems, be difficult to control, the Liquid Membrane System problem of unstable that runs off and to cause because of liquid film.
Summary of the invention
The dispersed and supported liquid membrane separating and recovering method that the purpose of this invention is to provide a heavy metal species, the Liquid Membrane System problem of unstable that the method that has solved existing hollow fiber renewal liquid membrane runs off and causes because of liquid film.
Technical scheme of the present invention is, the dispersed and supported liquid membrane separating and recovering method of a heavy metal species, and this method is implemented according to following steps:
Characteristics of the present invention also are,
The polymer support film is selected polypropylene screen, polyvinylidene fluoride film or poly tetrafluoroethylene for use, thickness 45 μ m, aperture 0.22～0.45 μ m, porosity 45～75%.
Liquid film solution is the mixed solution of flowing carrier and organic solvent, and wherein flowing carrier is selected P for use
204Or P
507, organic solvent is selected kerosene, benzinum or heptane for use.
The volume ratio that film is conciliate phase separation mutually is 3.75～4.25: 1.
For containing the organic solution of flowing carrier, flowing carrier is selected P for use to film mutually
507, organic solution is selected kerosene for use.
Separating phase separation is strong acid solution, selects sulfuric acid, hydrochloric acid or salpeter solution for use.
The invention has the beneficial effects as follows, do not need to add any surfactant, there is film to exist mutually in the decentralized photo, in the separated migrates process, because stirring action is constantly replenished the liquid film in the support membrane micropore, has kept the stability of supported liquid membrane system, improve membrane mass transfer efficient, thereby solved the Liquid Membrane System problem of unstable that runs off and cause because of liquid film in the supported liquid membrane technology.
Description of drawings
Fig. 1 is the used device schematic diagram of the inventive method embodiment.
Among the figure, 1. feed liquid pond, 2. the polymer support film is 3. resolved the pond, and 4. feed liquid pond agitator is 5. resolved pond agitator, 6. feed liquid phase, 7. decentralized photo.
The specific embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Fig. 1 is the used device of the inventive method embodiment (hereinafter to be referred as a SDLM migration cell) schematic diagram.Among the figure, hold the feed liquid phase 6 to be recycled that contains heavy metal ion in the feed liquid pond 1, hold by film in the parsing pond 3 that disperses to reclaim and conciliate the decentralized photo 7 that phase separation is formed mutually.In feed liquid pond 1 with resolve between the pond 3 and be provided with polymer support film 2, by polymer support film 2 with feed liquid mutually 6 and decentralized photo 7 at interval on both sides, in feed liquid pond 1, be provided with feed liquid pond agitator 4, in resolving pond 3, be provided with and resolve pond agitator 5.Feed liquid pond agitator 4 and parsing pond agitator 5 all adopt the controlled electric mixer of revolution.
Operation principle of the present invention is, liquid film phase high degree of dispersion is constituted decentralized photo in separating phase separation, utilizes the liquid film in the decentralized photo to make the liquid film that runs off in the polymer support membrane micropore obtain in time replenishing, and constitutes stable liquid film separating system.Decentralized photo is through after the simple static layering, and film can recycle use mutually, reclaims and separates phase separation, can reach to separate the purpose that reclaims heavy metal.
The technical solution used in the present invention may further comprise the steps:
During sample analysis,, the concentration of feed liquid phase is measured with AAS or polarography for single metal ion; Can select for use 520 type MPT Atomic Emission Spectrometer AESs that the concentration of feed liquid phase is measured for separating recovery hybrid metal ion.
Film in the inventive method after the separation recovery layering can be reused mutually.
In above-mentioned steps 1, polymer support film 2 can be selected polypropylene screen PP, polyvinylidene fluoride film PVDF or the poly tetrafluoroethylene PTFE material of porous, thickness 45 μ m, aperture 0.22～0.45 μ m, porosity 45～75% for use.Liquid film solution is the mixed solution of flowing carrier and organic solvent, and flowing carrier is selected P for use
204Or P
507, organic solvent is selected kerosene, benzinum or heptane for use.
In above-mentioned steps 2, for containing the lean solution of heavy metal ion, its concentration is between 50～100ppm mutually for feed liquid.Decentralized photo is to separate phase separation and film mixed solution mutually, and wherein for containing the organic solution of flowing carrier, flowing carrier is selected P for use to film mutually
507, organic solution is selected kerosene for use; Separating phase separation is strong acid solution, selects sulfuric acid, hydrochloric acid or salpeter solution for use.
Reaction and the transition process of transition metal in the dispersed and supported liquid membrane system roughly is divided into following a few step:
1), the metal ion of feed liquid in mutually by feed liquid mutually and the water diffusion layer of film between mutually;
2), at water-film boundary, metal ion (M
2+) following complex reaction takes place with carrier (HR);
Wherein: subscript f-represents water, and subscript org represents the film phase.M
f 2+-bivalent metal ion; (HR) 2-main extractant that exists with dimeric forms in non-polar oil.
3), the metal ion-carrier complex of previous step generation spreads mutually at film;
4), metal ion-carrier complex is diffused into and separates phase separation, with back washing agent following reaction takes place;
Wherein: bottom right mark S-back extraction decentralized photo.
5), carrier returns liquid phase and film boundary.
At first PVDF polymer support film 2 being placed concentration is 10% P
507Leaching absorption 4h blots the liquid on support membrane 2 surfaces then in the-kerosin with filter paper, and it is fixedly mounted in the middle of the SDLM migration cell as dividing plate.Getting cupric concentration is the analog electrical waste electroplating solution 200ml of 100ppm, is added in the feed liquid pond 1, and the pH that controls feed liquid phase 6 with HAc～NaAc cushioning liquid is 5.25; Get concentration and be 10% P
507-kerosin 160ml is added to and resolves in the pond 3, adds the parsing agent of the 4mol/L HCL of 40ml then in resolving pond 3 again.Start agitator, make feed liquid pond agitator 4 rotating speeds be controlled at 1400r/min, resolve pond agitator 5 rotating speeds and be controlled at 1400r/min.Every interval 20min sampling is a developer with 4-(2-pyridylazo)-resorcinol (PAR), and AAS is analyzed it.The result shows: as migration 2h, can reach more than 96% the rate of recovery of copper.
At first PTFE polymer support film 2 being placed concentration is 12% P
507Soak 3h in the-kerosin, blot the liquid on support membrane 2 surfaces then with filter paper, it is fixedly mounted in the middle of the SDLM migration cell as dividing plate.Get and contain the analog electrical waste electroplating solution 200ml that nickel concentration is 100ppm, be added in the feed liquid pond 1, with HAc～NaAc cushioning liquid control feed liquid mutually 6 pH be 5.0; Get concentration and be 12% P
507-kerosin 150ml is added to and resolves in the pond 3, adds the parsing agent of the 3mol/L HCL of 40ml then in resolving pond 3 again.Start agitator, feed liquid pond agitator 4 rotating speeds are controlled at about 1200r/min, resolve pond agitator 5 rotating speeds and be controlled at about 1000r/min.Every interval 30min sampling is a developer with PAR, and AAS is analyzed it.The result shows: as migration 2h, can reach more than 96% the rate of recovery of nickel.
At first PVDF polymer support film 2 being placed concentration is 10% P
204Soak 2h in the-kerosin, blot the liquid on support membrane 2 surfaces then with filter paper, it is fixedly mounted in the middle of the SDLM migration cell as dividing plate.Get and contain the analog electrical waste electroplating solution 200ml that zinc concentration is 50ppm, be added in the feed liquid pond 1, with HAc～NaAc cushioning liquid control feed liquid mutually 6 pH be 4.00; Get concentration and be 10% P
507-kerosin 160ml is added to and resolves in the pond 3, adds the parsing agent of the 2mol/L nitric acid of 40ml then in resolving pond 3 again.Start agitator, make feed liquid pond agitator 4 rotating speeds be controlled at 1200r/min, resolve pond agitator 5 rotating speeds and be controlled at 1200r/min.Every interval 10min sampling is a developer with PAR, and AAS is analyzed it.The result shows: as migration 2h, can reach more than 96% the rate of recovery of zinc.
Embodiment 4
At first PP polymer support film 2 being placed concentration is 15% P
507Soak 2h in the-kerosin, blot the liquid on support membrane 2 surfaces then with filter paper, it is fixedly mounted in the middle of the SDLM migration cell as dividing plate.Get and contain the analog electrical waste electroplating solution 200ml that cadmium concentration is 70ppm, be added in the feed liquid pond 1, with HAc～NaAc cushioning liquid control feed liquid mutually 6 pH be 5.0; Get concentration and be 15% P
507-kerosin 170ml is added to and resolves in the pond 3, adds the parsing agent of the 4mol/LHCL of 40ml then in resolving pond 3 again.Start agitator, make feed liquid pond agitator 4 rotating speeds be controlled at 1200r/min, resolve pond agitator 5 rotating speeds and be controlled at 1000r/min.Every interval 30min sampling is analyzed it with polarography.The result shows: as migration 2h, can reach more than 96% the rate of recovery of cadmium.
At first PVDF polymer support film 2 being placed concentration is 10% P
204Soak 2h in the-kerosin, blot the liquid on support membrane 2 surfaces then with filter paper, it is fixedly mounted in the middle of the SDLM migration cell as dividing plate.Get and contain the analog electrical waste electroplating solution 200ml that lead concentration is 80ppm, be added in the feed liquid pond 1, with HAc～NaAc cushioning liquid control feed liquid mutually 6 pH be 5.20; Get concentration and be 10% P
507-kerosin 160ml is added to and resolves in the pond 3, adds the parsing agent of the 3mol/L sulfuric acid of 40ml then in resolving pond 3 again.Start agitator, control feed liquid pond agitator 4 rotating speeds are that 1200r/min, parsing pond agitator 5 rotating speeds are 1200r/min.Every interval 30min sampling is a developer with PAR, and AAS is analyzed it.The result shows: as migration 2h, can reach more than 96% the rate of recovery of lead.
At first PVDF polymer support film 2 being placed concentration is 15% P
507Soak 2h in the-kerosin, blot the liquid on support membrane 2 surfaces then with filter paper, it is fixedly mounted in the middle of the SDLM migration cell as dividing plate.Get the hybrid analog-digital simulation electroplating wastewater solution 200ml that cupric, zinc concentration are 50ppm respectively, be added in the feed liquid pond 1, with HAc～NaAc cushioning liquid control feed liquid mutually 6 pH be 4.5; Get concentration and be 10% P
507-kerosin 160ml is added to and resolves in the pond 3, adds the parsing agent of the 3.5mol/L HCL of 40ml then in resolving pond 3 again.Start agitator, control feed liquid pond agitator 4 rotating speeds at 1200r/min, resolve pond agitator 5 rotating speeds at 1200r/min.Every interval 25min sampling is measured it with 520 type MPT Atomic Emission Spectrometer AESs.The result shows: as migration 2h, can reach more than 90% the migration of zinc, and the migration of copper is had only 5%, thereby realize separating and recovery zinc and copper.
At first PTFE polymer support film 2 being placed concentration is 15% P
204Soak 3h in the-n-heptane solution, blot the liquid on support membrane 2 surfaces then with filter paper, it is fixedly mounted in the middle of the SDLM migration cell as dividing plate.Get respectively and contain the hybrid analog-digital simulation electroplating wastewater solution 200ml that zinc, cadmium concentration are 50ppm, be added in the feed liquid pond 1, with HAc～NaAc cushioning liquid control feed liquid mutually 6 pH be 4.8; Get concentration and be 12% P
507-kerosin 150ml is added to and resolves in the pond 3, adds the parsing agent of the 3.2mol/L nitric acid of 40ml then in resolving pond 3 again.Start agitator, control feed liquid pond agitator 4 rotating speeds at 1400r/min, resolve pond agitator 5 rotating speeds at 1400r/min.Every interval 20min sampling is measured it with 520 type MPT Atomic Emission Spectrometer AESs.The result shows: as migration 2h, can reach more than 90% the migration of zinc, and the migration of cadmium is had only 5%, thereby realize separating and recovery zinc and cadmium.
Embodiment 8
At first PVDF polymer support film 2 being placed concentration is 15% P
507Soak 2.5h in the-kerosin, blot the liquid on support membrane 2 surfaces then with filter paper, it is fixedly mounted in the middle of the SDLM migration cell as dividing plate.Get respectively and contain the hybrid analog-digital simulation electroplating wastewater solution 200ml that zinc, lead concentration are 50ppm, be added in the feed liquid pond 1, with HAc～NaAc cushioning liquid control feed liquid mutually 6 pH be 4.2; Get concentration and be 15% P
507-kerosin 170ml is added to and resolves in the pond 3, adds the parsing agent of the 4mol/L nitric acid of 40ml then in resolving pond 3 again.Start agitator, make feed liquid pond agitator 4 rotating speeds, resolve pond agitator 5 rotating speeds at 1300r/min at 1300r/min.Every interval 10min sampling is measured it with 520 type MPT Atomic Emission Spectrometer AESs.The result shows: as migration 2h, can reach more than 90% the migration of zinc, and the migration of lead is had only 5%, thereby realize separating and recovery zinc and lead.
Embodiment 9
At first PP polymer support film 2 being placed concentration is 12% P
204Soak 4h in the-petroleum ether solution, blot the liquid on support membrane 2 surfaces then with filter paper, it is fixedly mounted in the middle of the SDLM migration cell as dividing plate.With cupric, nickel, zinc, the analog electrical waste electroplating solution of lead and cadmium ion is added in the feed liquid pond 1 successively, and the pH that controls feed liquid phase 6 with HAc～NaAc cushioning liquid is 5.0; Get concentration and be 12% P
507-kerosin 160ml is added to and resolves in the pond 3, adds the parsing agent of the 4mol/L sulfuric acid of 40ml then in resolving pond 3 again.Start agitator, make feed liquid pond agitator 4 rotating speeds be controlled at 1500r/min, resolve pond agitator 5 rotating speeds and be controlled at 1500r/min.Every interval 20min sampling is a developer with 4-(2-pyridylazo)-resorcinol (PAR), and AAS is analyzed it.The result shows: behind migration 2h, can reach more than 96% the rate of recovery of these five kinds of metals.
Embodiment 10
At first PVDF polymer support film 2 being placed concentration is 10% P
507Soak 2h in the-kerosin, blot the liquid on support membrane 2 surfaces then with filter paper, it is fixedly mounted in the middle of the SDLM migration cell as dividing plate.To contain zinc/copper, the analog electrical waste electroplating solution of zinc/cadmium and zinc/lead ion is added in the feed liquid pond 1 in the dispersed and supported liquid membrane device successively, with HAc～NaAc cushioning liquid control feed liquid mutually 6 pH be 5.25; Get concentration and be 15% P
507-kerosin 155ml is added to and resolves in the pond 3, adds the parsing agent of the 4mol/L HCL of 40ml then in resolving pond 3 again.Start agitator, make feed liquid pond agitator 4 rotating speeds be controlled at 1200r/min, resolve pond agitator 5 rotating speeds and be controlled at 1200r/min.Every interval 30min sampling is measured it with 520 type MPT Atomic Emission Spectrometer AESs.The result shows: as migration 2h, can reach more than 90% the migration of zinc, and to copper, cadmium and plumbous migration have only 5%, thereby realized to zinc and copper cadmium and plumbous separation and recovery.
Method of the present invention utilizes polymer as support membrane, rationally controls the composition and the content of each phase component, does not need to add any surfactant, just film is dispersed in mutually and separates in the phase separation, has avoided miscellaneous operations such as system breast, breakdown of emulsion in the emulsion liquid film partition method; There is film to exist mutually in the decentralized photo, in the separated migrates process, because stirring action, liquid film in the support membrane micropore is constantly replenished, the stability that has kept the supported liquid membrane system, improve membrane mass transfer efficient, thereby solved the Liquid Membrane System problem of unstable that runs off and cause because of liquid film in the supported liquid membrane technology.
Claims (6)
1, the dispersed and supported liquid membrane separating and recovering method of a heavy metal species is characterized in that: this method is implemented according to following steps:
Step 1, film preliminary treatment: with concentration is that 10%～15% liquid film solution soaked the polymer support film 2～4 hours, blot the liquid on polymer support film surface then, this polymer support film is placed in the separate tank, separate tank is partitioned into the feed liquid pond and resolves the pond;
Step 2, liquid film migration: the feed liquid that will contain heavy metal ion is injected in the feed liquid pond mutually, and the pH that controls the feed liquid phase with HAc～NaAc cushioning liquid is 4.00～5.25;
Take by weighing concentration more respectively and be 10%～15% film mutually and concentration be that the phase separation separated of 2mol/L～4mol/L injects in the parsing pond, combined group becomes decentralized photo, feed liquid liquid level mutually is in same horizontal plane in the liquid level that makes decentralized photo and the feed liquid pond;
Feed liquid pond and parsing pond are stirred, and every interval 10～30min sample analysis is resolved the concentration in pond;
Step 3, separation are reclaimed: according to the sampling result in last step, when the concentration of resolving the pond reaches recovery concentration, stop to stir, leave standstill decentralized photo, make the decentralized photo layering, be divided into the film phase on upper strata and the water of lower floor, water wherein is and separates the heavy metal ion solution that reclaims.
2, method according to claim 1 is characterized in that: in step 1, described polymer support film is selected polypropylene screen, polyvinylidene fluoride film or poly tetrafluoroethylene for use, thickness 45 μ m, aperture 0.22～0.45 μ m, porosity 45～75%.
3, method according to claim 1 is characterized in that: in step 1, described liquid film solution is the mixed solution of flowing carrier and organic solvent, and wherein flowing carrier is selected P for use
204Or P
507, organic solvent is selected kerosene, benzinum or heptane for use.
4, method according to claim 1 is characterized in that: in step 2, the volume ratio that described film is conciliate phase separation mutually is 3.75～4.25: 1.
5, method according to claim 1 is characterized in that: in step 2, for containing the organic solution of flowing carrier, flowing carrier is selected P for use to described film mutually
507, organic solution is selected kerosene for use.
6, method according to claim 1 is characterized in that: in step 2, the described phase separation of separating is a strong acid solution, selects sulfuric acid, hydrochloric acid or salpeter solution for use.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560604B (en) * | 2009-05-15 | 2010-11-10 | 西安理工大学 | Heavy metal ionic liquid chunk liquid film separating and recycling method |
| CN102154548A (en) * | 2011-03-18 | 2011-08-17 | 中国科学院地理科学与资源研究所 | Device and method for migration by adopting carrier mixed dual-phase sheet type combined liquid film |
| CN102633393A (en) * | 2011-02-15 | 2012-08-15 | 同济大学 | Nanotechnology integral treating device for inorganic/ organic waste water |
| CN104759444A (en) * | 2015-03-12 | 2015-07-08 | 湖南省同力电子废弃物回收拆解利用有限公司 | Comprehensive recycle treatment method of waste liquid crystal display (LCD) secondary resources |
| CN110791649A (en) * | 2018-08-01 | 2020-02-14 | 南开大学 | Method for preparing nano material from metal in electronic waste |
| CN111285499A (en) * | 2020-03-21 | 2020-06-16 | 哈尔滨工程大学 | Flat-plate liquid membrane supporting device suitable for high-level radioactive liquid waste separation and separation method |
| CN113634126A (en) * | 2021-08-14 | 2021-11-12 | 江苏华晖环保科技有限公司 | Magnesium chloride solution liquid membrane separation treatment device and process |
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2008
- 2008-05-29 CN CN2008100183280A patent/CN101284212B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560604B (en) * | 2009-05-15 | 2010-11-10 | 西安理工大学 | Heavy metal ionic liquid chunk liquid film separating and recycling method |
| CN102633393A (en) * | 2011-02-15 | 2012-08-15 | 同济大学 | Nanotechnology integral treating device for inorganic/ organic waste water |
| CN102633393B (en) * | 2011-02-15 | 2013-10-23 | 同济大学 | Nanotechnology integral treating device for inorganic/ organic waste water |
| CN102154548A (en) * | 2011-03-18 | 2011-08-17 | 中国科学院地理科学与资源研究所 | Device and method for migration by adopting carrier mixed dual-phase sheet type combined liquid film |
| CN104759444A (en) * | 2015-03-12 | 2015-07-08 | 湖南省同力电子废弃物回收拆解利用有限公司 | Comprehensive recycle treatment method of waste liquid crystal display (LCD) secondary resources |
| CN104759444B (en) * | 2015-03-12 | 2017-04-12 | 湖南省同力电子废弃物回收拆解利用有限公司 | Comprehensive recycle treatment method of waste liquid crystal display (LCD) secondary resources |
| CN110791649A (en) * | 2018-08-01 | 2020-02-14 | 南开大学 | Method for preparing nano material from metal in electronic waste |
| CN111285499A (en) * | 2020-03-21 | 2020-06-16 | 哈尔滨工程大学 | Flat-plate liquid membrane supporting device suitable for high-level radioactive liquid waste separation and separation method |
| CN113634126A (en) * | 2021-08-14 | 2021-11-12 | 江苏华晖环保科技有限公司 | Magnesium chloride solution liquid membrane separation treatment device and process |
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| CN101284212B (en) | 2011-05-04 |
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